U.S. patent application number 15/377666 was filed with the patent office on 2017-03-30 for humic acid derivatives and methods of preparation and use.
This patent application is currently assigned to EMPIRE TECHNOLOGY DEVELOPMENT LLC. The applicant listed for this patent is EMPIRE TECHNOLOGY DEVELOPMENT LLC. Invention is credited to Georgius Abidal ADAM, Anita NEEDHAM.
Application Number | 20170088528 15/377666 |
Document ID | / |
Family ID | 51989207 |
Filed Date | 2017-03-30 |
United States Patent
Application |
20170088528 |
Kind Code |
A1 |
ADAM; Georgius Abidal ; et
al. |
March 30, 2017 |
HUMIC ACID DERIVATIVES AND METHODS OF PREPARATION AND USE
Abstract
Disclosed are antioxidative natural compounds, their salts,
chelates and cleavage derivatives that exhibit a superior
combination of properties. The compounds can be used for a variety
of purposes, including the stabilization of polymers. The compounds
can be prepared by substantially cleaving a humic acid of formula I
followed by esterification to provide at least one antioxidant
compounds of formula V, formula VI, formula VII, formula VIII,
salts thereof, or chelates thereof.
Inventors: |
ADAM; Georgius Abidal;
(Edensor Park, AU) ; NEEDHAM; Anita; (Mangerton,
AU) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
EMPIRE TECHNOLOGY DEVELOPMENT LLC |
Wilmington |
DE |
US |
|
|
Assignee: |
EMPIRE TECHNOLOGY DEVELOPMENT
LLC
Wilmington
DE
|
Family ID: |
51989207 |
Appl. No.: |
15/377666 |
Filed: |
December 13, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14894660 |
Nov 30, 2015 |
9556134 |
|
|
PCT/US2013/042814 |
May 28, 2013 |
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15377666 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09K 15/06 20130101;
C07D 265/38 20130101; C08K 5/1535 20130101; C09K 15/30 20130101;
C07D 307/91 20130101; C07D 413/14 20130101; C07D 307/77 20130101;
C08K 5/357 20130101 |
International
Class: |
C07D 265/38 20060101
C07D265/38; C09K 15/06 20060101 C09K015/06; C08K 5/1535 20060101
C08K005/1535; C09K 15/30 20060101 C09K015/30; C07D 307/77 20060101
C07D307/77; C08K 5/357 20060101 C08K005/357 |
Claims
1. A stabilizing compound comprising at least one humic acid
derivative, wherein the humic acid derivative is selected from the
group consisting of formula VI, formula VII, and formula VIII:
##STR00010## R.sub.2 is hydrogen, --(C.sub.1-C.sub.20)alkyl, or
substituted --(C.sub.1-C.sub.20)alkyl; R.sub.4 is hydrogen,
--(C.sub.1-C.sub.20)alkyl, or substituted
--(C.sub.1-C.sub.20)alkyl; R.sub.11 is --N(R.sub.111)(R.sub.112),
wherein R.sub.111 is C-acetamido or substituted C-acetamido;
R.sub.112 is hydrogen, --(C.sub.1-C.sub.20)alkyl, substituted
--(C.sub.1-C.sub.20)alkyl, --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or
substituted --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; R.sub.21,
R.sub.22, R.sub.31, R.sub.32, and R.sub.41 are independently
hydrogen, --(C.sub.4-C.sub.20)alkyl, or substituted
--(C.sub.4-C.sub.20)alkyl; R.sub.23, R.sub.24, R.sub.25, R.sub.26,
R.sub.27, R.sub.33, R.sub.34, R.sub.35, R.sub.36, R.sub.42,
R.sub.43, and R.sub.44 are independently hydrogen,
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or substituted
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; and and wherein at least one
of R.sub.21, R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26, and
R.sub.27 is not hydrogen; at least one of R.sub.31, R.sub.32,
R.sub.33, R.sub.34, R.sub.35, and R.sub.36, is not hydrogen; and at
least one of R.sub.41, R.sub.42, R.sub.43, and R.sub.44 is not
hydrogen; a salt, chelate, or combination thereof.
2. The compound of claim 1, wherein the humic acid derivative of
formula VI, formula VII, formula VIII, a salt, chelate, or
combination thereof comprises: R.sub.2 is hydrogen or
--(C.sub.1-C.sub.20 alkyl; R.sub.23, R.sub.24, R.sub.25, R.sub.26,
and R.sub.27, are independently hydrogen or
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; R.sub.4 is hydrogen or
--(C.sub.1-C.sub.20)alkyl; R.sub.41 is independently hydrogen or
--(C.sub.4-C.sub.20)alkyl; and R.sub.42, R.sub.43, and R.sub.44 are
independently hydrogen or --(C.dbd.O)--(C.sub.3-C.sub.19 alkyl,
wherein at least one of R.sub.21, R.sub.22, R.sub.23, R.sub.24,
R.sub.25, R.sub.26, R.sub.27, R.sub.41, R.sub.42, R.sub.43, and
R.sub.44 is not hydrogen.
3.-6. (canceled)
7. The compound of claim 1, wherein the the humic acid derivative
comprises formula VI, a salt thereof, or chelate thereof.
8.-9. (canceled)
10. The compound of claim 1, wherein R.sub.2 is methyl.
11. The compound of claim 1, wherein R.sub.21, R.sub.22, are
independently hydrogen or --(C.sub.4-C.sub.20)alkyl.
12. The compound of claim 1, wherein R.sub.23, R.sub.24, R.sub.25,
R.sub.26, and R.sub.27, are independently hydrogen or
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; and wherein at least one of
R.sub.21, R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26, and
R.sub.27 is not hydrogen.
13. The compound of claim 1, wherein the humic acid derivative is
formula VII, a salt thereof, or chelate thereof.
14.-16. (canceled)
17. The compound of claim 1, wherein the humic acid derivative is
formula VIII, a salt thereof, or chelate thereof.
18-22. (canceled)
23. The compound of claim 1, wherein the salt is selected from the
group consisting of a lithium salt, a sodium salt, an ammonium
salt, a potassium salt, a calcium salt, a barium salt, a magnesium
salt, a manganese salt, a zinc salt, ab aluminum salt, and an iron
salt, or a combination thereof.
24. (canceled)
25. The compound of claim 1, wherein the humic acid derivative is a
polyvalent cation chelate.
26. The compounds of claim 1, wherein the humic acid derivative is
independently a calcium chelate, magnesium chelate, iron chelate,
or zinc chelate or combination thereof.
27. A method of preparing a polymer stabilizing mixture of
compounds, the method comprising: substantially hydrolyzing a humic
acid to form a mixture of compounds according to formula VI,
formula VII and formula VIII, a salt, chelate or combination
thereof: ##STR00011## wherein: R.sub.2 is hydrogen,
--(C.sub.1-C.sub.20)alkyl, or substituted
--(C.sub.1-C.sub.20)alkyl; R.sub.4 is hydrogen, --(C.sub.1-C.sub.20
alkyl, or substituted --(C.sub.1-C.sub.20)alkyl; R.sub.11 is
--N(R.sub.111)(R.sub.112), wherein R.sub.111 is C-acetamido or
substituted C-acetamido; R.sub.112 is hydrogen,
--(C.sub.1-C.sub.20)alkyl, substituted --(C.sub.1-C.sub.20)alkyl,
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or substituted
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; R.sub.21, R.sup.22, R.sub.31,
R.sub.32, and R.sub.41 are independently hydrogen,
--(C.sub.4-C.sub.20 )alkyl, or substituted
--(C.sub.4-C.sub.20)alkyl; R.sub.23, R.sub.24, R.sub.25, R.sub.26,
R.sub.27, R.sub.33, R.sub.34, R.sub.35, R.sub.36, R.sub.42,
R.sub.43, and R.sub.44 are independently hydrogen,
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or substituted
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; wherein at least one of
R.sub.21, R.sub.22, R23, R24, R.sub.25, R.sub.26, and R.sub.27 is
not hydrogen; at least one of R.sub.31, R.sub.32, R.sub.33,
R.sub.34, R.sub.35, and R.sub.36, is not hydrogen; and at least one
of R.sub.41, R.sub.42, R.sub.43, and R.sub.44 is not hydrogen; and
esterifying at least one functional group of the mixture of
compounds to give a polymer stabilizing mixture of compounds.
28. (canceled)
29. The method of claim 27, wherein esterifying comprises forming a
--(C.dbd.O)--(C3-C19)alkyl ester of at least one of R23, R24, R25,
R26, R27, R33, R34, R35, R36, R42, R43, and R44, to give an
esterified mixture.
30. The method of any one of claims 27, wherein esterifying
comprises forming a --(C4-C20)alkyl ester of at least one of R21,
R22, R31, R32, and R41, to give an esterified mixture.
31. (canceled)
32. The method of claim 27, further comprising forming a chelate of
at least one compound of the polymer stabilizing mixture with a
calcium cation, magnesium cation, zinc cation, iron cation, or
combinations thereof.
33. (canceled)
34. The method of claim 27, further comprising forming a salt of at
least one compound of the polymer stabilizing mixture to form a
lithium salt, sodium salt, ammonium salt, potassium salt, calcium
salt, barium salt, magnesium salt, manganese salt, zinc salt,
aluminum salt, iron salt, or a combination thereof.
35. The method of claim 27, further comprising purifying at least
one compound of the polymer stabilizing mixture.
36.-37. (canceled)
38. The method of claim 27, further comprising isolating a compound
of the polymer stabilizing mixture of formula VI wherein at least
one of R.sub.21, R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26,
and R.sub.27 is not hydrogen.
39. The method of claim 27, further comprising isolating a compound
of the polymer stabilizing mixture of formula VII wherein at least
one of R.sub.31, R.sub.32, R.sub.33, R.sub.34, R.sub.35, and
R.sub.36, is not hydrogen.
40. The method of claim 27, further comprising isolating a compound
of the polymer stabilizing mixture of formula VIII wherein at least
one of R.sub.41, R.sub.42, R.sub.43, and R.sub.44 is not
hydrogen.
41. The method of claim 27, wherein the humic acid comprises at
least one compound of formula I: ##STR00012## salt or chelate
thereof, wherein R.sub.11 is --N(R.sub.111)(R.sub.112), wherein
R.sub.111 is C-acetamido or substituted C-acetamido; R.sub.112 is
hydrogen, --(C.sub.1-C.sub.20)alkyl, substituted
--(C.sub.1-C.sub.20)alkyl, --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or
substituted --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; R.sub.12 is
hydrogen, --(C.sub.1-C.sub.20)alkyl, or substituted
--(C.sub.1-C.sub.20)alkyl; R.sub.13 is hydrogen,
--(C.sub.1-C.sub.20)alkyl, substituted --(C.sub.1-C.sub.20)alkyl,
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or substituted
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; and R.sub.16 is a hydrogen,
glucuronate or substituted glucuronate.
42. The method of claim 27, wherein the hydrolyzing comprises
hydrolyzing in the presence of an alkaline solution.
43. The method of claim 42, wherein the alkaline solution is
aqueous lithium hydroxide, aqueous sodium hydroxide, aqueous
potassium hydroxide, or combination thereof.
44. The method of claim 27, wherein the hydrolyzing comprises
hydrolyzing at a pH of 8.5-13.
45. (canceled)
46. A polymeric matrix comprising at least one stabilizing compound
of formula VI, formula VII, and formula VIII: ##STR00013## wherein:
R.sub.2 is hydrogen, --(C.sub.1-C.sub.20)alkyl, or substituted
--(C.sub.1-C.sub.20)alkyl; R.sub.4 is hydrogen,
--(C.sub.1-C.sub.20)alkyl, or substituted
--(C.sub.1-C.sub.20)alkyl; R.sub.11 is --N(R.sub.111)(R.sub.112),
wherein R.sub.111 is C-acetamido or substituted C-acetamido;
R.sub.112 is hydrogen, --(C.sub.1-C.sub.20)alkyl, substituted
--(C.sub.1-C.sub.20)alkyl, --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or
substituted --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; R.sub.21,
R.sub.22, R.sub.31, R.sub.32, and R.sub.41 are independently
hydrogen, --(C.sub.4-C.sub.20)alkyl, or substituted
--(C.sub.4-C.sub.20)alkyl; R.sub.23, R.sub.24, R.sub.25, R.sub.26,
R.sub.27, R.sub.33, R.sub.34, R.sub.35, R.sub.36, R.sub.42,
R.sub.43, and R.sub.44 are independently hydrogen,
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or substituted
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; and wherein at least one of
R.sub.21, R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26, and
R.sub.27 is not hydrogen; at least one of R.sub.31, R.sub.32,
R.sub.33, R.sub.34, R.sub.35, and R.sub.36, is not hydrogen; or at
least one of R.sub.41, R.sub.42, R.sub.43, and R.sub.44 is not
hydrogen; a salt thereof, chelate thereof, or combination thereof;
in combination with a polymer.
47. The polymeric matrix of claim 46, wherein the polymer is a
polyvinyl chloride, low density polyethylene, high density
polyethylene, polyvinyl alcohol, polypropylene, or combination
thereof.
48. (canceled)
49. The polymeric matrix of claim 46, wherein the at least one
stabilizing compound is present in the polymeric matrix at a
concentration of about 0.1% to about 0.5% of the total weight of
the polymer.
50. (canceled)
51. The polymeric matrix of claim 46, wherein the at least one
stabilizing compound comprises a lithium salt, sodium salt,
ammonium salt, potassium salt, calcium salt, barium salt, magnesium
salt, manganese salt, zinc salt, aluminum salt, iron salt, or a
combination thereof.
52. (canceled)
53. The polymeric matrix of claim 46, wherein the at least one
stabilizing compound comprises a magnesium chelate, calcium
chelate, zinc chelate, iron chelate, or combination thereof.
54. (canceled)
Description
BACKGROUND
[0001] Polymers and their composites are the essential materials
used in food packaging, medical applications, children toys,
teaching aids and other consumer goods. Processing of polymers to
the final products by all available technologies require using
several types of additives such as stabilizers, plasticizers,
fillers, anti-slippage, anti-static charges and others.
[0002] The plastics industry is searching for natural additives
such as stabilizers, plasticizer, antistatic charges and
antioxidants to stabilize polymers used in food packaging and the
other applications mentioned above to replace the currently used
anti-oxidants like BHT (butylated hydroxy toluene), TBHQ (tertiary
butylhydroquinone), BHA (butylated hydroxyl anisole) and synthetic
plasticizers such as DOP (dioctyl phthalate).
SUMMARY
[0003] New antioxidants for use in food packaging, medical
applications, children's toys and teaching aids are ideally
non-toxic as they are in direct contact with humans, inexpensive,
effective at low concentrations, and able to survive processing
such as injection, blow, extrusion or film production. The
additives in the finished products can be non-volatile, anti-static
and devoid of undesirable color, flavor, and odor effects. The
additives can also be compatible with ubiquitous polymer and can be
multi-functional additives such as stability effect; being a
thermal stabilizer, antioxidant, plasticize, anti-slippage, and
anti-static at the same time.
[0004] This disclosure details a natural source of inexpensive
additives that can be used in food packaging as well as other
applications where the plastic materials are in direct contact with
humans or other animals. The additives disclosed may function as
stabilizers, antioxidants, plasticizers, and/or convey anti-static
properties to the end product. The additives are at least inspired
by or based on humic acid, its cleaved products and their
derivatives such as salts and chelates as a multi-activity
stabilizer, antioxidant, chain breaking, free radical scavenger,
HCL acceptor for PVC and its copolymers, and an active plasticizer
with possible links with aseptic ingredients.
[0005] It has been found that subjecting humic acid to selective
aryl ether cleavage conditions followed by esterification and
chelate formation creates compounds that meet at least one, and
sometimes many or all the above described criteria for polymer
additives. The stabilization, plasticization and antistatic
efficiency of these sustainable natural products and their
derivatives is due to their chemical structure which contains all
functional groups that are known as antioxidants, free radical
scavengers active groups plus having synergistic characteristics
via o,p-quinone-hydroquinone structures, HCl deactivating agents
for PVC via metal chelates, promising plasticizing agents in
addition of being antistatic agents (which prevents dust
accumulation) due to high polar phenolic hydroxyl and ester groups.
The natural ingredient (humic acid) is currently produced on an
industrial scale for various applications. The low molecular weight
structures obtained from cleavage of humic acid have tremendous
potential as stabilizers, anti-oxidant/thermal stabilizers,
plasticizers for various polymer systems, particularly food-safe
polymeric packaging, medical applications and children toys, due to
their high stabilization efficiency, high decomposition
temperature, non-volatility, non-leachability and high chemical
stability, natural source, cheap and non-toxic.
[0006] The stabilizing compounds are ester derivatives of humic
acid I, or ester derivatives of hydrolysis products II, III, and IV
of humic acid I. The esters are alkyl esters or substituted alkyl
esters of the carboxylic acid moieties of humic acid, or the fatty
esters or substituted fatty esters of phenol moieties of humic acid
as esters V, VI, VII, and VIII. Various embodiments include
chelates and salts of the ester derivatives.
[0007] The polymer stabilizing compounds can be prepared by
substantially hydrolyzing humic acid to form a mixture of compounds
and esterifying at least one functional group of the mixture of
compounds to give a polymer stabilizing mixture of compounds.
Embodiments of the method further comprise formation of chelates or
salts of the compounds. Other embodiments further comprise
purification of one or more of the ester components.
[0008] Polymeric matrices comprise at least one of the polymer
stabilizing compounds. In certain embodiments, the polymeric matrix
can be of polyvinyl chloride, low density polyethylene, high
density polyethylene, polyvinyl alcohol, polypropylene, or a
combination thereof. The polymeric matrix can be used in a food
packaging, nutritional product packaging, beverage packaging, toy,
medical packaging, or cosmetic packaging.
DETAILED DESCRIPTION
[0009] The above summary of the present technology is not intended
to describe each illustrated embodiment or every possible
implementation of the present technology. The detailed description,
which follows, particularly exemplifies these embodiments.
[0010] Before the present compositions and methods are described,
it is to be understood that they are not limited to the particular
compositions, methodologies or protocols described, as these may
vary. It is also to be understood that the terminology used in the
description is for the purpose of describing the particular
versions or embodiments only, and is not intended to limit their
scope which will be limited only by the appended claims.
[0011] It must also be noted that as used herein and in the
appended claims, the singular forms "a", "an", and "the" include
plural reference unless the context clearly dictates otherwise.
Unless defined otherwise, all technical and scientific terms used
herein have the same meanings as commonly understood by one of
ordinary skill in the art. Although any methods and materials
similar or equivalent to those described herein can be used in the
practice or testing of embodiments disclosed, the preferred
methods, devices, and materials are now described.
[0012] The term "alkyl" or "alkyl group" refers to a branched or
unbranched hydrocarbon or group of 1 to 20 carbon atoms, such as
but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, t-butyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl,
tetracosyl and the like. "Cycloalkyl" or "cycloalkyl groups" are
branched or unbranched hydrocarbons in which all or some of the
carbons are arranged in a ring, such as but not limited to
cyclopentyl, cyclohexyl, methylcyclohexyl and the like. The term
"lower alkyl" includes an alkyl group of 1 to 6 carbon atoms.
[0013] "Substituent" refers to a molecular non-toxic group that
replaces a hydrogen in a compound and may include, but is not
limited to, C.sub.1-C.sub.20 alkyl. The term "substituted alkyl" is
used herein to allow for the presence of one or more additional
substituents on an alkyl group.
[0014] "Optional" or "optionally" means that the subsequently
described event or circumstance may or may not occur, and that the
description includes instances where the event occurs and instances
where it does not.
[0015] The term "halide" as used herein refers to the halogens
fluorine, chlorine, bromine, and iodine.
[0016] "Substantially no" means that the subsequently described
event may occur at most about less than 10% of the time or the
subsequently described component may be at most about less than 10%
of the total composition, in some embodiments, and in others, at
most about less than 5%, and in still others at most about less
than 1%.
[0017] As used herein the term `transition metal" should be
understood to include elements that are non-toxic non heavy metals
or radioactive of the Periodic Table. In chemical terms, these are
elements having a partially filled inner shell of electrons. The
term "transition metal chelate" as used herein generally means a
transition metal cation and anions that surround the metal cation
and are joined to it by electrostatic bonds.
[0018] As used herein, the term "stereoisomer" refers to a compound
made up of the same atoms bonded by the same bonds but having
different three-dimensional structures which are not
interchangeable.
[0019] Humic acid having chemical structure (I), wherein
##STR00001##
[0020] R.sub.11 is --N(R.sub.111)(R.sub.112), wherein R.sub.111 is
C-acetamido or substituted C-acetamido; R.sub.112 is hydrogen,
--(C.sub.1-C.sub.20)alkyl, substituted --(C.sub.1-C.sub.20)alkyl,
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or substituted
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl;
[0021] R.sub.12 is hydrogen, --(C.sub.1-C.sub.20)alkyl, or
substituted --(C.sub.1-C.sub.20)alkyl;
[0022] R.sub.13 is hydrogen, --(C.sub.1-C.sub.20)alkyl, substituted
--(C.sub.1-C.sub.20)alkyl, --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or
substituted --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; and
[0023] R.sub.16 is a hydrogen, glucuronate or substituted
glucuronate,
[0024] has cleavable groups at C1-C4.
[0025] Hydrolysis of aryl heteroatom bonds C1-C4 of humic acid I
leads to compounds II-IV. The compounds are active multi pH buffers
since they dissolve at all pH values. The cleavage derivatives of
humic acid at one or more of C1-C4, and their carboxylate salts and
chelates have lower molecular weight than humic acid. These
derivatives also have high oxygen content due to carboxylate groups
adjacent to carbonyl or hydroxyl groups.
##STR00002##
[0026] salt, or chelate thereof, wherein [0027] R.sub.2 is
hydrogen, --(C.sub.1-C.sub.20)alkyl, or substituted
--(C.sub.1-C.sub.20)alkyl; and [0028] R.sub.4 is hydrogen,
--(C.sub.1-C.sub.20)alkyl, or substituted
--(C.sub.1-C.sub.20)alkyl.
[0029] Polymer stabilizing compounds may be prepared as ester
derivatives of humic acid I, or ester derivatives of hydrolysis
products II, III, and IV of humic acid I. The esters are alkyl
esters or substituted alkyl esters of the carboxylic acid moieties,
or the fatty esters or substituted fatty esters of phenol moieties
of humic acid.
[0030] In an aspect, the stabilizing compound is an ester of at
least one of formulas V-VIII:
##STR00003##
[0031] R.sub.2 is hydrogen, --(C.sub.1-C.sub.20)alkyl, or
substituted --(C.sub.1-C.sub.20)alkyl;
[0032] R.sub.4 is hydrogen, --(C.sub.1-C.sub.20)alkyl, or
substituted --(C.sub.1-C.sub.20)alkyl;
[0033] R.sub.11 is --N(R.sub.111)(R.sub.112), wherein R.sub.111 is
C-acetamido or substituted C-acetamido; R.sub.112 is hydrogen,
--(C.sub.1-C.sub.20)alkyl, substituted --(C.sub.1-C.sub.20)alkyl,
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or substituted
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl;
[0034] R.sub.12, R.sub.141, R.sub.142, R.sub.143, and R.sub.144,
are independently hydrogen, --(C.sub.1-C.sub.20)alkyl, or
substituted --(C.sub.1-C.sub.20)alkyl;
[0035] R.sub.13 is hydrogen, --(C.sub.1-C.sub.20)alkyl, substituted
--(C.sub.1-C.sub.20)alkyl, --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or
substituted --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl;
[0036] R.sub.16 is a hydrogen, glucuronate or substituted
glucuronate;
[0037] R.sub.21, R.sub.22, R.sub.31, R.sub.32, and R.sub.41 are
independently hydrogen, --(C.sub.4-C.sub.20)alkyl, or substituted
--(C.sub.4-C.sub.20)alkyl;
[0038] R.sub.23, R.sub.24, R.sub.25, R.sub.26, R.sub.27, R.sub.33,
R.sub.34, R.sub.35, R.sub.36, R.sub.42, R.sub.43, and R.sub.44 are
independently hydrogen, --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or
substituted --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; and
[0039] R.sub.151, R.sub.152, R.sub.153, R.sub.154, R.sub.1559 and
R.sub.156 are independently hydrogen,
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or substituted
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; and
[0040] wherein at least one of R.sub.141, R.sub.142, R.sub.143,
R.sub.144, R.sub.151, R.sub.152, R.sub.153, R.sub.154, R.sub.155,
and R.sub.156 is not hydrogen; at least one of R.sub.21, R.sub.22,
R.sub.23, R.sub.24, R.sub.25, R.sub.26, and R.sub.27 is not
hydrogen; at least one of R.sub.31, R.sub.32, R.sub.33, R.sub.34,
R.sub.35, and R.sub.36, is not hydrogen; and at least one of
R.sub.41, R.sub.42, R.sub.43, and R.sub.44 is not hydrogen;
[0041] a salt, chelate, or combination thereof.
[0042] An embodiment is a compound wherein the compound is at least
one chemical formula of VI-VIII, salt, chelate, or combination
thereof.
[0043] One embodiment is at least one compound with formula V-VIII,
wherein the compound is a salt. In another embodiment, the salt is
a lithium salt, sodium salt, ammonium salt, potassium salt, calcium
salt, barium salt, magnesium salt, manganese salt, zinc salt,
aluminum salt, iron salt, or a combination thereof. In yet another
embodiment, the salt is a sodium salt, potassium salt, calcium
salt, or ammonium salt. In still another embodiment the compound is
a polyvalent cation chelate. In another embodiment, the chelate is
a calcium, magnesium, iron, or zinc chelate or combination
thereof.
[0044] Another embodiment is a compound wherein the compound is of
chemical formula of VI, salt, chelate, or combination thereof,
wherein:
[0045] R.sub.2 is hydrogen, --(C.sub.1-C.sub.20)alkyl, or
substituted --(C.sub.1-C.sub.20)alkyl;
[0046] R.sub.21, R.sub.22, are independently hydrogen,
--(C.sub.4-C.sub.20)alkyl, or substituted
--(C.sub.4-C.sub.20)alkyl;
[0047] R.sub.23, R.sub.24, R.sub.25, R.sub.26, and R.sub.27, are
independently hydrogen, --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or
substituted --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; and
[0048] wherein at least one of R.sub.21, R.sub.22, R.sub.23,
R.sub.24, R.sub.25, R.sub.26, and R.sub.27 is not hydrogen. Another
embodiment is the compound wherein R.sub.2 is hydrogen or
--(C.sub.1-C.sub.20)alkyl. In certain embodiments, R.sub.2 is
methyl. In other embodiments, R.sub.21, R.sub.22, are independently
hydrogen or --(C.sub.4-C.sub.20)alkyl. In other embodiments,
wherein R.sub.23, R.sub.24, R.sub.25, R.sub.26, and R.sub.27, are
independently hydrogen or --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; and
wherein at least one of R.sub.21, R.sub.22, R.sub.23, R.sub.24,
R.sub.25, R.sub.26, and R.sub.27 is not hydrogen.
[0049] Another embodiment is at least one compound of formula VI,
wherein the compound is a salt. In another embodiment, the salt is
a lithium salt, sodium salt, ammonium salt, potassium salt, calcium
salt, barium salt, magnesium salt, manganese salt, zinc salt,
aluminum salt, iron salt, or a combination thereof. In yet another
embodiment, the salt is a sodium salt, potassium salt, calcium
salt, or ammonium salt. In still another embodiment, at least one
compound of formula VI is a polyvalent cation chelate. In another
embodiment, the chelate is a calcium, magnesium, iron, or zinc
chelate or combination thereof.
[0050] Another embodiment the compound has formula VII, salt,
chelate, or combination thereof, wherein
[0051] R.sub.31, R.sub.32, are independently hydrogen,
--(C.sub.4-C.sub.20)alkyl, or substituted
--(C.sub.4-C.sub.20)alkyl;
[0052] R.sub.33, R.sub.34, R.sub.35, and R.sub.36, are
independently hydrogen, --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or
substituted --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; and
[0053] wherein at least one of R.sub.31, R.sub.32, R.sub.33,
R.sub.34, R.sub.35, and R.sub.36 is not hydrogen. Another
embodiment is the compound wherein further R.sub.31 and R.sub.32,
are independently hydrogen or --(C.sub.4-C.sub.20)alkyl, and
wherein at least one of R.sub.31, R.sub.32, R.sub.33, R.sub.34,
R.sub.35, and R.sub.36 is not hydrogen. Another embodiment is the
compound wherein R.sub.33, R.sub.34, R.sub.35, and R.sub.36 are
independently hydrogen or --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, and
wherein at least one of R.sub.31, R.sub.32, R.sub.33, R.sub.34,
R.sub.35, and R.sub.36 is not hydrogen.
[0054] Another embodiment is at least one compound of formula VII,
wherein the compound is a salt. In another embodiment, the salt is
a lithium salt, sodium salt, ammonium salt, potassium salt, calcium
salt, barium salt, magnesium salt, manganese salt, zinc salt,
aluminum salt, iron salt, or a combination thereof. In yet another
embodiment, the salt is a sodium salt, potassium salt, calcium
salt, or ammonium salt. Still another embodiment is at least one
compound of formula VII, wherein the compound is a polyvalent
cation chelate. In another embodiment, the chelate is a calcium,
magnesium, iron, or zinc chelate or combination thereof.
[0055] An embodiment is a compound wherein the compound is of
chemical formula of VIII, salt, chelate, or combination thereof,
wherein
[0056] R.sub.4 is hydrogen, --(C.sub.1-C.sub.20)alkyl, or
substituted --(C.sub.1-C.sub.20)alkyl;
[0057] R.sub.41 is independently hydrogen,
--(C.sub.4-C.sub.20)alkyl, or substituted
--(C.sub.4-C.sub.20)alkyl;
[0058] R.sub.42, R.sub.43, and R.sub.44 are independently hydrogen,
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or substituted
--(C.dbd.O)--(C.sub.3-C.sub.19) alkyl; and
[0059] wherein at least one of R.sub.41, R.sub.42, R.sub.43, and
R.sub.44 is not hydrogen. Another embodiment is the compound
wherein further R.sub.4 is hydrogen or --(C.sub.1-C.sub.20)alkyl. A
certain embodiment is wherein R.sub.4 is methyl. Another embodiment
is wherein R.sub.41 is hydrogen or --(C.sub.4-C.sub.20)alkyl, and
wherein at least one of R.sub.41, R.sub.42, R.sub.43, and R.sub.44
is not hydrogen. Still another embodiment is wherein R.sub.42,
R.sub.43, and R.sub.44 are independently hydrogen or
--(C.dbd.O)--(C3-C19)alkyl, and wherein at least one of R.sub.41,
R.sub.42, R.sub.43, and R.sub.44 is not hydrogen.
[0060] Another embodiment is at least one compound of formula VIII,
wherein the compound is a salt. In another embodiment, the salt is
a lithium salt, sodium salt, ammonium salt, potassium salt, calcium
salt, barium salt, magnesium salt, manganese salt, zinc salt,
aluminum salt, iron salt, or a combination thereof. In yet another
embodiment, the salt is a sodium salt, potassium salt, calcium
salt, or ammonium salt. Still another embodiment is at least one
compound of formula VIII, wherein the compound is a polyvalent
cation chelate. In another embodiment, the chelate is a calcium,
magnesium, iron, or zinc chelate or combination thereof.
[0061] Another aspect is a method to prepare a stabilizing compound
from humic acid. A representative humic acid (I):
##STR00004##
[0062] salt, or chelate thereof, wherein
[0063] R.sub.11 is --N(R.sub.111)(R.sub.112), wherein R.sub.111 is
C-acetamido or substituted C-acetamido; R.sub.112 is hydrogen,
--(C.sub.1-C.sub.20)alkyl, substituted --(C.sub.1-C.sub.20)alkyl,
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or substituted
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl;
[0064] R.sub.12 is hydrogen, --(C.sub.1-C.sub.20)alkyl, or
substituted --(C.sub.1-C.sub.20)alkyl;
[0065] R.sub.13 is hydrogen, --(C.sub.1-C.sub.20)alkyl, substituted
--(C.sub.1-C.sub.20)alkyl, --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or
substituted --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; and
[0066] R.sub.16 is a hydrogen, glucuronate or substituted
glucuronate.
[0067] Is cleaved at C1-C4 to give cleavage products (II-IV):
##STR00005##
[0068] salt, or chelate thereof, wherein
[0069] R.sub.2 is hydrogen, --(C.sub.1-C.sub.20)alkyl, or
substituted --(C.sub.1-C.sub.20)alkyl; and
[0070] R.sub.4 is hydrogen, --(C.sub.1-C.sub.20)alkyl, or
substituted --(C.sub.1-C.sub.20)alkyl. Humic acid I and cleavage
products II-IV are contacted with an agent to give fatty acid
esters V-VIII.
##STR00006##
[0071] salt, or chelate thereof, wherein
[0072] R.sub.11 is --N(R.sub.111)(R.sub.112), wherein R.sub.111 is
C-acetamido or substituted C-acetamido; R.sub.112 is hydrogen,
--(C.sub.1-C.sub.20)alkyl, substituted --(C.sub.1-C.sub.20)alkyl,
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or substituted
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl;
[0073] R.sub.12, R.sub.141, R.sub.142, R.sub.143, and R.sub.144 are
independently hydrogen, --(C.sub.1-C.sub.20)alkyl, or substituted
--(C.sub.1-C.sub.20)alkyl;
[0074] R.sub.13 is hydrogen, --(C.sub.1-C.sub.20)alkyl, substituted
--(C.sub.1-C.sub.20)alkyl, --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or
substituted --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl;
[0075] R.sub.151, R.sub.152, R.sub.153, R.sub.154, R.sub.155, and
R.sub.156 are independently hydrogen,
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or substituted
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; and
[0076] R.sub.16 is a hydrogen, glucuronate or substituted
glucuronate;
[0077] wherein at least one of R.sub.141, R.sub.142, R.sub.143,
R.sub.144, R.sub.151, R.sub.152, R.sub.153, R.sub.154, R.sub.155,
and R.sub.156 is not hydrogen;
##STR00007##
[0078] R.sub.2 is hydrogen, --(C.sub.1-C.sub.20)alkyl, or
substituted --(C.sub.1-C.sub.20)alkyl;
[0079] R.sub.4 is hydrogen, --(C.sub.1-C.sub.20)alkyl, or
substituted --(C.sub.1-C.sub.20)alkyl;
[0080] R.sub.21, R.sub.22, R.sub.31, R.sub.32, and R.sub.41 are
independently hydrogen, --(C.sub.4-C.sub.20)alkyl, or substituted
--(C.sub.4-C.sub.20)alkyl;
[0081] R.sub.23, R.sub.24, R.sub.25, R.sub.26, R.sub.27, R.sub.33,
R.sub.34, R.sub.35, R.sub.36, R.sub.42, R.sub.43, and R.sub.44 are
independently hydrogen, --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or
substituted --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; and
[0082] wherein at least one of R.sub.21, R.sub.22, R.sub.23,
R.sub.24, R.sub.25, R.sub.26, and R.sub.27 is not hydrogen, at
least one of R.sub.31, R.sub.32, R.sub.33, R.sub.34, R.sub.35, and
R.sub.36, is not hydrogen, and at least one of R.sub.41, R.sub.42,
R.sub.43, and R.sub.44 is not hydrogen.
[0083] In another embodiment the compound has a formula V. In
another embodiment, the compound has a formula VI. In yet another
embodiment, the compound has a formula VII. In still another
embodiment, the compound has a formula VIII.
[0084] In the various embodiments, the agent is a reactive fatty
acid equivalent, wherein at least one aryl alcohol forms an alkyl
ester. In some embodiments, the fatty acid equivalent is an acid
chloride. In other embodiments, the fatty acid equivalent is an
anhydride. In still other embodiments, the fatty acid is an
activated ester. In certain embodiments, the alkyl ester formed is
a --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl fatty ester.
[0085] In the various embodiments, the agent is an alcohol, wherein
at least one carboxylic acid functionality forms an alkyl ester. In
some embodiments, the carboxylic acid is activated as an acid
chloride. In other embodiments, the carboxylic acid is activated as
an anhydride. In still other embodiments, the carboxylic acid is an
activated ester. In yet other embodiments, the carboxylic acid is
esterified general acid or base catalysis. In still other
embodiments, the alkyl ester is from a transesterification. In
certain embodiments, the alkyl ester formed is a
--(C.sub.4-C.sub.20)alkyl ester.
[0086] In the various embodiments, the agent is a first agent and a
second agent. In some embodiments, the first agent is an alcohol as
above and a second agent is a reactive fatty acid equivalent as
above.
[0087] In each of the embodiments, the method can further comprise
making at least one salt or chelate of the compounds. In an
embodiment of the salts, the method comprises making a lithium
salt, sodium salt, ammonium salt, potassium salt, calcium salt,
barium salt, magnesium salt, manganese salt, zinc salt, aluminum
salt, iron salt, or a combination thereof. In yet another
embodiment, the method comprises making a sodium salt, potassium
salt, calcium salt, or ammonium salt. In an embodiment of the
chelates, the method comprises making a polyvalent cation chelate.
In another embodiment, the method comprises making a calcium,
magnesium, iron, or zinc chelate or combination thereof.
[0088] In another embodiment, the method can further comprise
isolating at least one compound of formula V-VIII, salt, chelate,
or combination thereof. Isolation can include, but is not limited
to, filtration, decantation, phase separation, distillation,
centrifugation, evaporation, or combinations thereof.
[0089] In another embodiment, the method can further comprise
purifying at least one compound of formula V-VIII, salt, chelate,
or combination thereof. Purification can include, but is not
limited to, steam distillation, distillation, crystallization,
reverse phase chromatography, normal phase chromatography,
precipitation, refining, sublimation, evaporation, extraction,
absorption, washing, or combinations thereof.
[0090] In various embodiments the humic acid I may be cleaved at
positions C1, C2, C3, and C4 by action of a hydrogenolysis cleaving
agent. Hydrogenolysis cleaving agents can include, but are not
limited to nickel-catalyzed hydrogenolysis, sodium borohydride
(NaBH.sub.4), amide hydro halide salts, lithium chloride in
dimethylformamide, hydrogen iodide, and hydrogen bromide, and
others.
[0091] In various embodiments the hydrolysis is carried out in an
alkaline solution. In some embodiments, the alkaline solution is an
aqueous alkaline hydroxide, or mixtures thereof. In some
embodiments, the alkaline solution is aqueous lithium hydroxide,
aqueous sodium hydroxide, aqueous potassium hydroxide, or
combination thereof. In certain embodiments, the alkaline solution
is aqueous sodium hydroxide. In various embodiments, the hydrolysis
is performed at a pH of about 8, about 8.5, about 9, about 10,
about 11, about 12, about 13, about 14, or at a pH range between or
at any of the two pH values. In various embodiments, the hydrolysis
is performed with heat. In certain embodiments, the hydrolysis is
performed at reflux temperatures.
[0092] Still another aspect is a polymeric matrix comprising at
least one stabilizing compound of formula V-VIII:
##STR00008##
[0093] wherein R.sub.2 is hydrogen, --(C.sub.1-C.sub.20)alkyl, or
substituted --(C.sub.1-C.sub.20)alkyl;
[0094] R.sub.4 is hydrogen, --(C.sub.1-C.sub.20)alkyl, or
substituted --(C.sub.1-C.sub.20)alkyl;
[0095] R.sub.11 is --N(R.sub.111)(R.sub.112), wherein R.sub.111 is
C-acetamido or substituted C-acetamido; R.sub.112 is hydrogen,
--(C.sub.1-C.sub.20)alkyl, substituted --(C.sub.1-C.sub.20)alkyl,
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or substituted
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl;
[0096] R.sub.12, R.sub.141, R.sub.142, R.sub.143, and R.sub.144 are
independently hydrogen, --(C.sub.1-C.sub.20)alkyl, or substituted
--(C.sub.1-C.sub.20)alkyl;
[0097] R.sub.13 is hydrogen, --(C.sub.1-C.sub.20)alkyl, substituted
--(C.sub.1-C.sub.20)alkyl, --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or
substituted --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl;
[0098] R.sub.16 is a hydrogen, glucuronate or substituted
glucuronate;
[0099] R.sub.21, R.sub.22, R.sub.31, R.sub.32, and R.sub.41 are
independently hydrogen, --(C.sub.4-C.sub.20)alkyl, or substituted
--(C.sub.4-C.sub.20)alkyl;
[0100] R.sub.151, R.sub.152, R.sub.153, R.sub.154, R.sub.1559 and
R.sub.156 are independently hydrogen,
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or substituted
--(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; and
[0101] R.sub.23, R.sub.24, R.sub.25, R.sub.26, R.sub.27, R.sub.33,
R.sub.34, R.sub.35, R.sub.36, R.sub.42, R.sub.43, and R.sub.44 are
independently hydrogen, --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl, or
substituted --(C.dbd.O)--(C.sub.3-C.sub.19)alkyl; and
[0102] wherein at least one of R.sub.141, R.sub.142, R.sub.143,
R.sub.144, R.sub.151, R.sub.152, R.sub.153, R.sub.154, R.sub.155,
and R.sub.156 is not hydrogen; at least one of R.sub.21, R.sub.22,
R.sub.23, R.sub.24, R.sub.25, R.sub.26, and R.sub.27 is not
hydrogen; at least one of R.sub.31, R.sub.32, R.sub.33, R.sub.34,
R.sub.35, and R.sub.36, is not hydrogen; and at least one of
R.sub.41, R.sub.42, R.sub.43, and R.sub.44 is not hydrogen; salt,
or chelate thereof;
[0103] in combination with a polymer.
[0104] In an embodiment the compound is at least one compound of
formula VI-VIII. In another embodiment the compound has a formula
V. In another embodiment, the compound has a formula VI. In yet
another embodiment, the compound has a formula VII. In still
another embodiment, the compound has a formula VIII.
[0105] Embodiments include a polymeric matrix comprising at least
one antioxidant compound of formula V-VIII, a salt, or chelate
thereof, in combination with a polymer. In certain embodiments, the
polymer is a polyvinyl chloride, low density polyethylene, high
density polyethylene, polyvinyl alcohol, polypropylene, or
combination thereof. In yet other embodiments, the polymeric matrix
may be suitable for various packaging to extend a shelf life of a
product. In certain embodiments, the polymeric matrix is a food
packaging, nutritional product packaging, beverage packaging, toy,
medical packaging, or cosmetic packaging.
[0106] In yet another embodiment, the antioxidant compound is
present in the polymeric matrix by weight at a concentration of
about 5%, about 2.5%, about 1%, about 0.5%, about 1000 ppm, about
300 ppm, about 200 ppm, about 100 ppm, about 30 ppm, about 10 ppm,
about 3 ppm, about 1 ppm, or any range between two of the
concentrations. In various specific embodiments, the antioxidant is
present in a polymer at less than about 5000 ppm, less than about
300 ppm, less than about 100 ppm, or less than about 10 ppm. In
certain embodiments, the antioxidant compound is between about
0.02% and about 2.5% by weight of the polymer. In another certain
embodiment, the antioxidant compound is between about 0.1% and
about 0.5% by weight.
[0107] In each of the aforementioned embodiments of the polymeric
matrix, the antioxidant compound may be a salt. In certain
embodiments, the salt is a lithium salt, sodium salt, ammonium
salt, potassium salt, calcium salt, barium salt, magnesium salt,
manganese salt, zinc salt, aluminum salt, iron salt, or a
combination thereof. In certain embodiments, the salt is a sodium
salt, potassium salt, calcium salt, ammonium salt, or combination
thereof. In an embodiment, the antioxidant compound is a sodium
salt. In another embodiment, the antioxidant compound is a
potassium salt. In yet another embodiment, the antioxidant compound
is a calcium salt. In still another certain embodiment, the
antioxidant compound is an ammonium ion salt. In yet other
embodiments of the aforementioned antioxidant compounds, the
antioxidant compound may be a polyvalent chelate. In certain
embodiments, the transition metal ion chelate is a magnesium
chelate, calcium chelate, zinc chelate, iron chelate, or
combination thereof.
[0108] The chelates of fatty ester products V-VIII are particularly
suitable as HCl deactivators for PVC and its copolymers. The
chelates can react with HCl formed from the thermal decomposition
of PVC. The role of HCl is well known to accelerate the thermal
decomposition of PVC (accordingly PVC stabilizers consist of HCl
deactivators (Scheme 1):
##STR00009##
[0109] In some embodiments, the fatty ester products V-VIII can be
transferred to master batch pellets which can be added to any
thermoplastic or elastomers during their processing to the final
packaging products. Master batch is a technical method to improve
distribution and homogenization of the additives within a polymeric
matrix. In a master batch, most of the active ingredients, except
the plasticizers, used in small composition ratios such as
colorants, stabilizers, antistatic materials and other additives
are extruded with a high melt index polymer, for example, either
same polymer or from other compatible polymers, and then
transferred to a pellet form that which can be easily mixed with
the required basic polymer and processed to the final products.
[0110] The fatty ester products V-VIII represent ideal structures
as antistatic additives which are essential additives usually added
to most polymers in order to prevent the accumulation of dusts on
the surface of the packaged items such as: toys, medical packaging
and appliances and cosmetics which accordingly, leave the surface
clean of dust. The efficiency of these materials as anti-static
additives is based on the concept that preventing static charge
accumulation, by either using conductive materials such as
quaternary ammonium salts or by using compounds with highly polar
groups that are capable of forming hydrogen bonding or having
electrolyte characteristics. The new natural derivatives described
in this disclosure possess the characteristics which make packing
anti-static: that being they consist of metal chelates and have
free hydroxyl groups that form strong hydrogen bonding.
[0111] The fatty ester products V-VIII are very efficient
multi-functional plasticizing additives and are highly suitable to
replace the currently used phthalate plasticizers due to the
current global health issues surrounding these plasticizers. The
advantage of the new natural based plasticizers over the phthalate
plasticizers is that they are non-toxic and based on aromatic
structures which give them enhanced compatibility with most common
polymers used in thermoplastic industry for packaging. They possess
extremely high boiling point and thus are almost non-volatile, and
have high molecular weight which leads them to be non-migratable,
non-leachable, and have high thermal stability. In other wards it
has almost all the requirement of plasticizers for various
applications with the added advantage of being non-toxic and food
grade as the starting materials are based on natural food
ingredient.
[0112] A typical esterification reaction of the phenolic groups
present in the natural humic antioxidant cleavage product and fatty
carboxylic acids such as octanoic acid, iso-octanoic acid, butanoic
acid, decanoic acid, or other carboxylic acids with alkyl groups
containing: C.sub.4 to C.sub.20. Typical esterfication reaction of
the carboxylic acids, carboxylic acid anhydride or acid chlorides
with phenolic groups present in the natural antioxidant and fatty
alcohols such as butyl alcohol, pentyl, hexyl, heptyl, cetyl, to
C.sub.20. The same reactions can be applied to humic acid I, and
its cleavage derivatives II-IV to prepare mono, di, tri, or oligo
ester groups, and as partially chelated with suitable metal
ions.
[0113] Cleavage of aryl heteroatom bonds C1-C4 of humic acid I
leads to compounds II-IV. The compounds are active multi pH buffers
since they dissolve at all pH values. The cleavage derivatives of
humic acid at one or more of C1-C4, and their carboxylate salts and
chelates have lower molecular weight than humic acid. These
derivatives also have high oxygen content due to carboxylate groups
adjacent to carbonyl or hydroxyl groups.
[0114] Humic acid cleavage derivatives can be obtained by a
reductive cleavage technique. Chemical compounds V-VIII, have
active functional groups (quinones, hydroquinones and alkyl
phenols) that can act as anti-oxidants and free radical scavengers,
chelating groups (via carboxyl groups or hydroxyl groups). The
chemical compounds V-VIII are less expensive to manufacture than
ascorbic acid and have the ability to dissolve and bond minerals
and other nutritional elements with enhanced bioavailability.
[0115] The anti-oxidation efficiency of these sustainable, natural
derivatives is due to their chemical structure which contains
functional groups that are known as antioxidants and free radical
scavenger active groups. Humic acid as a basic ingredient for the
proposed technology is currently extracted on industrial scale
mainly for use as organic fertilizers and plant nutrients. It is
sourced cheaply from non-contaminated marsh and forest soils that
can contain up to 30-40% humic materials. Furthermore, these
compounds have tremendous potential as thermal stabilizers for
various polymer systems used in food packaging.
[0116] The cleavage derivatives of humic acid I have various uses
including as antioxidants for several polymeric systems such as
polyvinyl chloride (PVC), polyethylene (PE) and polypropylene (PP).
These antioxidants can be used as a solid, solution, chelated with
transition (nutrient) metals. The carboxylic acid group can be
transformed into carboxylate salts of Na, K, Ca, Zn, Mg, and can
form chelates with divalent and trivalent metal ions. The low
molecular weight structures derived demonstrate a higher efficiency
as anti-oxidants than humic acid I, and the chemical compounds
V-VIII have tremendous potential as anti-oxidant/thermal
stabilizers for various polymer systems, particularly food-safe
polymeric packaging.
[0117] The antioxidants of embodiments from cleavage of humic acid
typically require no necessary purification steps, such as
ultrafiltration or desalination, nor fractionation into fractions
with distinct molecular weights and high purity. The crude
antioxidant cleavage solution unexpectedly, and advantageously,
exhibits high activity without any further costly processing.
However, purified compounds, their salts, chelates, and cleavage
derivatives can potentially exhibit superior characteristics in
certain applications.
[0118] Consumer interest in and awareness of the health properties
of antioxidants has been increasing in recent years. This has
simultaneously increased global sales of antioxidants (whether used
as a food preservative or to provide a health enhancing or
functional benefit) and foods that are recognized as being
naturally rich in antioxidants. As the sector has developed,
antioxidants are now being used in the manufacture of a greater
variety of goods to cater for increasingly health-conscious
consumers.
[0119] The humic acid derivatives are more efficient (based on
humic acid studies) and cost effective compared to all other
plasticizers and stabilizers. Humic acid derivatives and cleavage
derivatives would be cheaper to manufacture than ascorbic acid and
synthetic antioxidants and have greater thermal stability
convenient for almost all food processing and cooking up to
350.degree. C. and have the ability to dissolve and bond minerals
and other nutritional elements with enhanced bioavailability.
EXAMPLES
[0120] Although the present technology has been described in
considerable detail with reference to certain embodiments thereof,
other versions are possible. Therefore the spirit and scope of the
appended claims should not be limited to the description and
versions contained within this specification. The various aspects
of the present technology will be illustrated with reference to the
following non-limiting examples.
Example 1
Cleavage of Humic Acid Using Sodium Hypophosphite and Hydrogen
Iodide
[0121] Humic acid was extracted from non-polluted marsh soils with
an organic content of 30-35%. The alkaline extracted humic acid
from marsh soils or forests soils was suspended in 25-40% HI
solution in a stoichiometric equivalent ratio to the ether groups
of humic acid weight ratio of 1:10. The humic acid underwent
cleavage in the presence of sodium hypophosphite (10% of the HI)
added to prevent further iodination of the aromatic phenolic
structures and prevents oxidation of iodine ions.
[0122] The reaction mixture was heated to reflux. The humic acid
suspension began to cleave after 45 minutes and the solution became
colored. The color changed progressively with reflux time.
Fractions were taken at 15 minute intervals until all the humic
acid suspension disappears (approximately after 10 hours depending
on the concentration of HI) until a homogeneous reaction mixture
was obtained.
[0123] Fraction products were neutralized or transferred to the
carboxylate salts (Na, Ca, Mg, Mn, and similar salts) by
neutralizing the carboxylic acid groups with required alkaline
hydroxides or carbonate.
[0124] The reaction matrix compositions mixture were characterized
by TLC (Thin Layer Chromatography), pH titration, IR, NMR and
molecular weight determination for some of the fractions.
[0125] The TLC displayed at least 12 spots using different solvent
carriers, indicating the presence of at least 12 compounds in the
final reaction mixture. This was in good agreement with the
chemical structure evaluation in addition of presence of low
aromatic carboxylic acids and hydroquinone derivatives.
Example 2a
Cleavage of Humic Acid Using Nickel Catalysis
[0126] The cleavage of bonds of Example 1 may be performed by
nickel catalyzed hydrogenolysis. The humic acid is dissolved in
3-octenone or other solvents or mixed solvents in the presence of
nickel carbine complex under one bar of hydrogen at a temperature
of 80-120.degree. C. The reaction produces a mixture of compounds
II-IV.
Example 2b
Cleavage of Humic Acid Using Sodium Borohydride
[0127] The cleavage of bonds of Example 1 may be performed by
action of sodium borohydride. Humic acid is dissolved in a solution
of sodium hydroxide in 1:1 ethanol: water in the presence of
Ni--Cr-boride where sodium borohydride is formed in situ. The
reaction takes place at atmospheric pressure. The reaction produces
a mixture of compounds II-IV.
Example 2c
Cleavage of Humic Acid Using Lithium Chloride
[0128] The cleavage of bonds of Example 1 may be performed by
action of lithium chloride in dimethyl formamide. Humic acid is
dissolved in a solution of LiCl--DMF at boiling conditions for 4-72
hours. The reaction produces a mixture of compounds II-IV.
Example 2d
Cleavage of Humic Acid Using Hydrogen Iodide
[0129] The cleavage of bonds of Example 1 may be performed by
action of hydrogen iodide. The humic acid is reacted with aqueous
hydrogen iodide and sodium hypophosphite to form a suspension.
Alternatively, the suspension is heated until a substantially
homogeneous reaction mixture is obtained. In yet another
alternative, the heating is carried out at reflux temperature. The
reaction produces a mixture of compounds
Example 2e
Cleavage of Humic Acid Using Hydrogen Bromide
[0130] The cleavage of bonds of Example 1 were performed by action
of hydrogen bromide. Humic acid was dissolved in an organic solvent
such as methyl ethyl ketone or a mixture of solvents, and then this
mixture was added to an aqueous solution consisting of glacial
acetic acid and concentrated hydrogen bromide at 0-10.degree. C. in
the presence of 1% surfactant (Cetrimide). The cleavage was carried
out in an emulsion system under efficient mixing for 5 hours. At
the end of five hours, the temperature was raised to 25.degree. C.
The reaction was continued for an additional hour. The reaction
produced a mixture of compounds II-IV.
Example 3a
Esterification of Compounds II-IV Phenols to Give Mixed Nonyl
Esters
[0131] Mixed acetic-nonanoic anhydride 12.5 gm is added to a 250 ml
stirred flask and 0.95 gm of a mixture of compounds II-IV from any
one of Examples 1 and 2a-2e and 0.13 gm sulphuric acid added to the
anhydride to form a mobile dispersion. This is heated to
90-100.degree. C. and maintained at this temperature for 3 hours
before cooling to 40.degree. C. and dispersion in 200 ml of ethanol
or petroleum ether. After filtration or concentration the solid is
subjected to two further washes before being dried and analyzed to
give a yield of 80% of mixed nonyl aryl esters of compounds
II-IV.
Example 3b
Esterification of Compound IV Phenols to Give Trinonyl Ester
VIII
[0132] Mixed acetic-nonanoic anhydride 12.5 gm is added to a 250 ml
stirred flask and 3.74 gm
2-(2,7,8-trihydroxy-1,4-dioxo-1H-phenoxazin-10(4H)-yl)propanoic
acid (IV, R=Me) and 0.13 gm sulphuric acid added to the anhydride
to form a mobile dispersion. This is heated to 90-100.degree. C.
and maintained at this temperature for 3 hours before cooling to
40.degree. C. and dispersion in 200 ml of ethanol or petroleum
ether. After filtration or concentration the solid is subjected to
two further washes before being dried and analyzed to give a yield
of 80% of the trinonyl aryl esters of compound IV.
Example 3c
Esterification of Compounds II-IV Carboxylic Acids to Give Mixed
Esters
[0133] One kg of a mixture of compounds II-IV, 1872 gm of decyl
alcohol (12 mol), and 0.59 gm of tetra butyl titanate are weighed
into a 4 liter distillation flask with a Dean-Stark-trap and reflux
condenser, and heated to boiling under nitrogen. The water of
reaction produced during the esterification is regularly removed.
After about 3 hours the excess alcohol is distilled off under
vacuum. The mixture is cooled to 80.degree. C. and transferred to a
4 liter reaction flask with immersion tube, dropping funnel, and
column A sodium hydroxide solution (5 weight %) is then used for
neutralization. The mixture is then heated under vacuum (10 mbar)
to 190.degree. C. Deionized water is then added drop-wise via the
dropping funnel, at constant temperature. After addition of the
water, the heating is switched off and the mixture is cooled. The
mixed esters are filtered with a filtration aid to give a mixture
of decyl carboxylic esters of compounds VI-VIII.
Example 3d
Esterification of Compound IV Carboxylic Acid to Give Decyl
Ester
[0134] Compound IV (100 gm), 187 gm of decyl alcohol, and 0.06 gm
of tetra butyl titanate are weighed into a 500 mL distillation
flask with a Dean-Stark-trap and reflux condenser, and heated to
boiling under nitrogen. The water of reaction produced during the
esterification is regularly removed. After about 3 hours excess
alcohol is distilled off under vacuum. The mixture is cooled to
80.degree. C. and transferred to a 500 mL reaction flask with
immersion tube, dropping funnel, and column. A sodium hydroxide
solution (5 weight %) is then used for neutralization. The mixture
is then heated under vacuum (10 mbar) to 190.degree. C. Deionized
water is then added drop-wise via the dropping funnel, at constant
temperature. After addition of the water, the heating is switched
off and the mixture is cooled. The mixed esters are filtered with a
filtration aid to form the decyl carboxylic ester of compound
VIII.
Example 4a
Preparation of the Calcium Chelates of a Mixture of Decyl Esters of
Compounds VI-VIII
[0135] Calcium oxide (5.6 gm) and 65 gm of the decyl esters of
compounds VI-VIII (Example 3c) were placed into a flask provided
with a reflux condenser. Ethanol (100 mL) was added and the mixture
was stirred and boiled at atmospheric pressure for 5 hours. The
reaction mixture was then cooled, and thereafter filtered yielding
65 grams of calcium chelate of the decyl esters having the physical
characteristic of a fine white powder.
Example 4b
Preparation of the Magnesium Chelate of Decyl Ester of Compound
VIII
[0136] 4.0 grams (0.1 Mole) of magnesium oxide and 65 grams (0.2
Mole) of the decyl ester of compound VIII (Example 3d) were placed
into a flask provided with a reflux condenser. Ethanol (100 mL) was
added and the mixture was stirred and boiled at atmospheric
pressure for 5 hours. The reaction mixture was then cooled, and
thereafter filtered yielding 60 grams of calcium chelate of the
decyl ester of compound VIII having the physical characteristic of
a fine white powder.
Example 4c
Preparation of the Zinc Chelate of Decyl Ester of Compound VII
[0137] Zinc hydroxide is placed in a flask with a reflux condenser
and 100 grams of the decyl ester of compound VII. Ethanol is added
and the mixture boiled for 3 hours. The mixture is cooled and
filtered yielding 100 gm of the zinc chelate of the decyl ester of
compound VII.
Example 5
Stability Data
[0138] The mixture of the calcium chelate of compounds of formula
V, VI, VII, and VIII prepared in Example 4, were evaluated as
antioxidants and thermal stabilizers for PVC, low density
polyethylene, and polyvinyl alcohol as a model to evaluate the
anti-oxidation efficiency using thermal analysis (differential
scanning calorimetry (DSC) and thermo gravimetric analysis (TGA))
techniques, including differential thermogravimetry (DTG) to
determine the decomposition temperature. The chelates with several
transition metal ions showed remarkable efficiency for
thermo-oxidative stabilization of PVC. Typical results are provided
in Table (1). Tests using 1% of the calcium salt of the hydrolyzed
humate mixture in extruded PVC show higher stabilizing efficiency
than 1% of humic acid in extruded PVC. Both were better than PVC
extruded without an antioxidant.
TABLE-US-00001 TABLE (1) Thermal degradation stability of PVC and
stabilized PVCs HCl % (loss) from TGA PVC with +1% Ca-chelate of a
mixture of PVC control PVC with 1% V, VI, VII, Temperature,
.degree. C. (K value 70) Humic acid and VIII 250 3 1 0 260 5 2 0
270 10 2 0.5 280 33 5 1.0 290 1 13 1.0 300 47 35 5.0 Total HCl loss
(%) at 63 57 53 Decomp. Temp. Decomp. Temp., .degree. C., 265 280
310 from DTG Rate of decomposition at 1.63 1.09 0.73 Decomp. Temp.
%/min
Example 6
Stabilization of Polyethylene for Food Packaging
[0139] Polyethylene films are prepared with 0.1% by weight and with
0.5% by weight of a mixture of the calcium chelate of compounds of
formula V, VI, VII, and VIII prepared in Example 4 by extrusion
methods to form films for food packaging. The films are subjected
to natural sun light in Sydney, Australia, and with high UV light
for 4 weeks. The resultant films are tested by IR and UV
spectrometry. The films stabilized with metal chelates show no
color change and no spectral changes, while unstabilized
polyethylene samples as controls show change in coloration and
absorption spectra.
Example 7
Stabilization of Polyvinyl Chloride (PVC) for Food Packaging
[0140] PVC (K value 70) stabilized with 1% of a mixture of the
calcium chelate of compounds of formula V, VI, VII, and VIII
prepared in Example 4 (typical thermal stability characteristics
listed in Table 1) are prepared by extrusion to form films for food
packaging. The films are subjected to natural sunlight in Sydney,
Australia, and with high UV light for 4 weeks. The stabilized films
with metal chelates show no color change while control films of
unstabilized PVC samples show change in coloration to a dark
yellowish color.
* * * * *